Phenylacetonitrile oximes



United States Patent 3,374,250 PHENYLACETONHTRILE OXIMES John S.Heekies, Lancaster, and Charles D. Mitchell,

Willow Street, Pa., assignors to Armstrong Cork Company, Lancaster, Pa,a corporation of Pennsylvania No Drawing. Filed Aug. 3, 1965, Ser. No.477,023 1 Claim. (Cl. 260-396) This invention relates tophenylacetonitrile oximes, and more particularly to such oximes whichcontain a substituted cyclohexadiene ring.

The phenylacetonitrile oximes of the present invention have the formulawherein X and Y are selected from the group consisting of H,

provided that Y is not and one and only one of X and Y is hydrogen.

The compounds are useful as ultraviolet light absorbers, particularlywhen distributed throughout a film of a thermoplastic resin such aspolyamides, the polycarbonates, or the acrylates. The phenylacetonitrileoximes of the present invention may be taken up in a suitable inertsolvent system which also contains the dissolved polymer. Bottles orother glass containers, 01' sheets of glass may then be coated in anyconvenient manner with the solution. On solution evaporation, a stable,ultraviolet light absorbing film will be left on the glass.

The following examples illustrate several embodiments of the invention.

EXAMPLE 1 Preparation of 3-phen0xy-4-0x0-a-phenyl-2,5-cycl0 hexadiene-A-acetoniirile oxime Into a 500 m1. four-necked flask, fitted withthermometer, stirrer, reflux condenser, and dropping funnel, was placeda solution of 25 g. (0.385 mole, assay 86.3%) of potassium hydroxidedissolved in 50 ml. of absolute methanol. The solution was colled to 10C., and 7.45 g. (0.064 mole) of benzyl cyanide was added in one portion.o-Nitrophenyl phenyl ether (13.56 g., 0.063 mole) was added dropwiseduring 5 minutes at C. with stirring. The deep red reaction mixture wasstirred and held at room temperature for 30 minutes with an ice bathuntil the initial exothermic reaction subsided. The mixture was thenstirred at room temperature an additional 3 /2 hours. During this time alarge amount of deep red solid separated. The addition of 200 ml. ofwater with cooling and stirring gave a cloudy solution which clearedwhen 50 ml. of absolute methanol was added. Acidification of the darkred solution with dilute acetic acid gave a bright yellow semi-solidwhich, when collected by filtration, dried in vacuo, and triturated withabsolute methanol, gave 16.5 g. (83%) of bright yellow solid, M.P.l35140. Yellow crystals of the pure 3,374,250 Patented Mar. 19, 1968oxime (M.P. 140141.2) were obtained after four recrystallizations frombenzene.

Calcd for C H N O C, 76.42; H, 4.49; N, 8.91. Found: C, 76.33; H, 4.29;N, 8.76.

EXAMPLE 2 Preparation of 2-phen0xy-4-0x0-a-phenyl-2,5- cyclohexadiene-A-acet0nitrile oxime Into a 500 m1. three-necked flask fitted withthermometer, stirrer, reflux condenser, and dropping funnel, was placeda solution of 25 g. (0.385 mole, assay 86%) of potassium hydroxidedissolved in 50 ml. of absolute methanol. To the cooled solution (10)was added in one portion 7.45 g. (0.063 mole) of benzyl cyanide followedby the dropwise addition of 13.56 g. (0.063 mole) of m-nitrophenylphenyl ether. The reaction temperature was held at room temperature byan ice bath until the initial exothermic reaction subsided. Within 30minutes a deep red solid precipitated. After stirring an additional 3 /2hours at room temperature a solution of 200 ml. absolute methanol andml. water was added while cooling and stirring. The deep red solutionwas pressure filtered through a sintered glass tube leaving 5.8 g. ofether soluble red tar in the reaction flask.

The deep red alkaline filtrate was washed twice with 50-ml. portions ofether. Acidification of the filtrate with dilute acetic acid gave 10.14g. of orange solid which, when collected by filtration, air dried, andtriturated with ether, gave 5.5 g. (28%) of crude yellow oxime, M.P.l58l60. Yellow crystals of the pure oxime (M.P. 161- 162) were obtainedafter five recrystallizations from benzene.

Calcd for C H N O C, 76.42; H, 4.49; N, 8.91. Found: C, 76.25; H, 4.32;N, 8.74.

EXAMPLE 3 Preparation 0 4-0x0-3-0-nitrophenyl-2,5-cycl0hexadiene- A"-acet0nitrile oxime Into a 500 ml. four-necked flask, fitted withreflux condenser, dropping funnei, stirrer, and thermometer, were placed25g. (0.385 mole) of potassium hydroxide (assay 86.3%) .and 50 ml. ofabsolute methanol. The mixture was stirred until the potassium hydroxidedissolved, then cooled to 20. Benzyl cyanide (9.14 g., 0.078 mole) wasadded in one portion followed by the addition of 8.03 g. (0.034 mole) of2,2'-dinitrobiphenyl in one portion through a powder funnel. The mixturebecame deep blue immediately. The reaction temperature was kept below 25C. during the addition of the nitro compound by an ice bath. The mixturewas stirred at 2025 for four hours during which time a small amount ofsolid and a large amount of tar separated making stirring difiicult.Water (250 ml.) was added and the mixture was stirred vigorously for 15minutes. The deep blue aqueous phase was decanted from the tar,filtered, washed with ether until the extracts were nearly colorless,and acidified with dilute acetic acid. The resulting pale yellow solid,when collected by filtration, washed with water, and dried in a vacuumdesiccator, gave 0.25 g. of solid A.

The tar was dissolved in benzene-the addition of a small amount ofacetic acid was necessary to achieve complete solution. The resultingdeep red benzene solution was extracted with 30-ml. portions of 5%potassium hydroxide until the extracts became colorless, washed withwater until neutral to litmus, and dried over anhydrous sodium sulfate.

The potassium hydroxide extracts were combined, washed with 50-ml.portions of ether until the ether washes became nearly colorless,filtered, and acidified with dilute acetic acid. The resulting paleyellow solid was collected by filtration, washed with water, and dried 3in a vacuum desiccator. The infrared spectra (IR of solids B and A areidentical and contain a moderate highly conjugated nitrile band at4.52;.i, a moderate broad hydroxyl band at 2.93 1, strong nitro bands at6.53 and 7.42,-i, and a strong 9.98 band.

EXAMPLE 4 Preparation of 3-benzyl-4-0xo-u-plzenyl-2,5-cyclohexadiene-A-acetonirrile oxime Into a 300 ml. three-necked flask, fitted withstirrer, dropping funnel, refiux condenser, and thermometer, was placeda solution of 12.5 g. (0.19 mole, assay 86.3%) of potassium hydroxidedissolved in ml. of absolute methanol. Benzyl cyanide (3.7 g., 0.032mole) was added in one portion at room temperature followed by the rapiddropwise addition of 6.6 g. (0.031 mole) of 2-nitrodiphenylmethane (B.P.117118 at 0.06 mm). The reaction temperature rose to a maximum of C. anda small amount of deep red solid precipitated. The deep red reactionmixture was stirred slowly for 3 /2 hours at room temperature, then 1hour at C. On cooling, a voluminous amount of deep red solidprecipitated. Methanol ml.) was added with vigorous stirring. Theresulting deep red solution was acidified with glacial acetic acid. Theaddition of 100 ml. of water caused a red oil to separate whichcrystallized on standing overnight. The crude oxime when collected byfiltration, washed with water, and air dried weighed 9.6 g. (99%).Yellow crystals of the pure oxime (M.P. 146-147.5) were obtained byrecrystallization from benzene. Its infrared spectrum Preparation of2-benzyl-4-0x0-a-phenyl-2,5-cycl0- hexadiene-a -acetonitrile oxime Intoa 300 ml. three-necked flask, fitted with thermometer, stirrer, droppingfunnel, and reflux condenser, was placed a solution of 12.5 g. (0.19mole, assay 86.3%) of potassium hydroxide dissolved in 25 m1. ofabsolute methanol. The solution was cooled to 10 C., and 3.7 g. (0.032mole) of benzyl cyanide was added in one portion. 3-nitrodiphenylmethane(B.P. 116-120 at 0.06 mm.) was added dropwise between 1020 with stirringand cooling. The deep red reaction mixture was stirred slowly for 4 /2hours at 25 C. Absolute methanol (100 ml.) was .added with rapidstirring and cooling. The resulting deep red mixture was acidified withglacial acetic acid, then filtered. Addition of water to the filtratecaused the crude oxime (9.5 g., 98%) to separate as a heavy oil.

Confirmation of structure is provided by its infrared spectrum whichcontains a strong broad hydroxyl band at 3.02 a moderate highlyconjugated nitrile band at 453 and a very strong band characteristic ofquinoid oximes at 10.10 1..

EXAMPLE 6 A resinous polycarbonate was prepared by the reaction ofphosgene and 4,4-bis(4-hydroxy phenyl) pentanoic acid. A film of thispolycarbonate was prepared containing 1.7% by weight 3-phenyl 4oxo-a-phenyl-2,5-cyclohexadiene-A -acetonitrile oxime and was placedunder ultraviolet light for 500 hours in a Weather-Ometer. After 500hours, the tensile strength of the fi'lm was 8,500 p.s.i., compared toan initial value of 10,000 p.s.i. A control film not containing theoxime was completely degraded and useless after the 500 hours exposurein the Weather- Ometer.

We claim:

1. Phenylacetonitrile oximes of the formula NO Ir wherein X and Y areselected from the group consisting of H,

provided that Y is not and one and only one of X and Y is hydrogen.

LORRAINE A. WEINBERGER, Primary Examiner.

L. A. THAXTON, Assistant Examiner.

1. PHENYLACETRONITRILE OXIMES OF THE FORMULA